CN107459959A - A kind of flexible package adhesive for solvent-free use of resistance to boiling and preparation method thereof - Google Patents

A kind of flexible package adhesive for solvent-free use of resistance to boiling and preparation method thereof Download PDF

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Publication number
CN107459959A
CN107459959A CN201710757420.8A CN201710757420A CN107459959A CN 107459959 A CN107459959 A CN 107459959A CN 201710757420 A CN201710757420 A CN 201710757420A CN 107459959 A CN107459959 A CN 107459959A
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China
Prior art keywords
component
solvent
boiling
free use
resistance
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CN201710757420.8A
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CN107459959B (en
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李永杰
田丛
黄建滔
刘瀛
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CHINA LUCKY Group Corp.
Shanghai Lekai New Material Technology Co.,Ltd.
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CHINA LUCKY GROUP Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/36—Hydroxylated esters of higher fatty acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
    • C08G18/4213—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from terephthalic acid and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
    • C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6629—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/08—Polyurethanes from polyethers

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention provides a kind of flexible package adhesive for solvent-free use of resistance to boiling, the adhesive includes component A and B component, component A is by polyester diol, at least two and diisocyanate cpd in polyether Glycols and vegetable oil polyol react obtained isocyanate terminated urethane prepolymer, B component is the polyol blends of polyether Glycols and/or polyether-tribasic alcohol and polyacrylate polyol composition, wherein, described 25 DEG C of viscosity of component A are 1000 4000mPa.s, its isocyanate groups weight content is 13% 18%, described 25 DEG C of viscosity of B component are 500 2000mPa.s, its hydroxyl value is 50 180mgKOH/g；Component A is with B component according to mol ratio NCO：OH=1.1 1.8：1 ratio is mixed, and viscosity of the obtained adhesive for solvent-free use at 35 45 DEG C is 500 800mPa.s.The present invention can provide composite membrane excellent curing peel strength, and composite membrane can still keep good peel strength after 30 minutes through 135 DEG C of boilings, and the material such as various plastic sheetings, aluminizer is compound suitable for the fields such as medicine, packaging for foodstuff, industrial packaging.

Description

A kind of flexible package adhesive for solvent-free use of resistance to boiling and preparation method thereof
Technical field
The present invention relates to a kind of adhesive for solvent-free use with superior adhesion energy and boiling resistance energy, invention adhesives It is applicable to the compound of the material such as various plastic sheetings, aluminizer in the fields such as medicine, packaging for foodstuff, industrial packaging.
Background technology
Adhesive for solvent-free use is the non-volatile green that one kind can be applied to composite, particularly package compound field Adhesive.During Material cladding, adhesive for solvent-free use does not produce toxic gas, is also not in that food, medicine etc. are poisonous The harm of dissolvent residual.Because using adhesive for solvent-free use, non-volatile thing produces in recombination process, thus can realize low energy consumption, It is compound under high speed.
A kind of adhesive for solvent-free use is disclosed in patent document CN96106661, uses acrylic ester monomer or vinyl The polymer of monomer mixes with PPG and/or PEPA, reacts the poly- of generation NCO end-blockings with isocyanate-monomer Urethane adhesive.Compared with unmodified polyurethane, the adhesive initial bonding strength is good, but adhesive viscosity at 100 DEG C is higher than 2000mPa.s, it is not easy to realize that low-temperature and high-speed is coated with, though the boiling resistance of adhesive is not directed in invention, one-component is without molten Agent adhesive is limited by its crosslink density and curing degree, and boiling resistance can be usually less than double component solvent-free adhesive.
A kind of no-solvent type Laminating adhesive is disclosed in patent document CN102604583, it is even by using silane in formula The polyalcohol that connection agent is modified improves the heat resistance and repellency of Laminating adhesive, and adhesive for solvent-free use prepared by this method is at 60 DEG C Viscosity is 1000mPa.s or so, it is compound after sample can keep good peel strength after 3 hours through 100 DEG C of boilings.Although the hair The adhesive coating performance being related in bright is preferable, but viscosity is higher, it is necessary to carried out under the conditions of at least 50 DEG C compound, and is only capable of It is resistant to 100 DEG C of boiling conditions.
At present using the coating weight of adhesive for solvent-free use compound tense generally in 0.8-2.0g/m2, Coating Speed 300- 500m/min, and the usual viscosity of adhesive with boiling resistance energy being related in the prior art is higher, need to be more than 50 DEG C Mixed glue, coating are carried out under temperature conditionss, its execution conditions requires higher.
As Food Packaging technology is gradually perfect, simplification and final production of the market to adhesive for solvent-free use coating process The boiling resistance of product can require also more and more higher, therefore, can be achieved can still have excellent stripping when compound low temperature and low coating weight The adhesive for solvent-free use of intensity and boiling resistance energy is the focus on research direction of this area.
The content of the invention
It is solvent-free viscous with resistance to boiling the invention provides a kind of flexible package for problem above existing for adhesive for solvent-free use Mixture, the adhesive can not only realize that low temperature is compound, and coating weight is high in peel strength, have resistance to 135 DEG C of thermophilic digestions Characteristic, it is applicable to the compound of the material such as various plastic sheetings, aluminizer in the fields such as medicine, food
In addition present invention also offers the preparation method of the above-mentioned adhesive of resistance to boiling.
The present invention solves the technical scheme that above-mentioned technical problem is provided：
A kind of flexible package adhesive for solvent-free use of resistance to boiling, it includes component A and B component, and wherein component A is included by polyester At least two polyol blends and diisocyanate cpd in dihydric alcohol, polyether Glycols and vegetable oil polyol react Obtained isocyanate terminated urethane prepolymer, B component are included by polyether Glycols and/or polyether-tribasic alcohol and polyacrylic acid The polyol blends of ester polyol composition.
The above-mentioned flexible package adhesive for solvent-free use of resistance to boiling, the component A include the polyester binary by 60-100 parts by weight The diisocyanate of at least two glycol compositions and 100 parts by weight in alcohol, polyether Glycols and vegetable oil polyol Compound reacts obtained isocyanate terminated urethane prepolymer, and component A viscosity at 25 DEG C is 1000-4000mPa.s；
In the polyol blends that the B component is included, polyol blends gross weight ratio is shared by each polyalcohol Polyether Glycols and/or polyether-tribasic alcohol 50%-70%, polyacrylate polyol 30%-50%；The B component is at 25 DEG C When viscosity be 500-2000mPa.s.
The above-mentioned flexible package adhesive for solvent-free use of resistance to boiling, the component A polyester diol can pass through dicarboxylic acids, aliphatic Glycol is made through polycondensation reaction,
Wherein, the dicarboxylic acids is aliphatic or the aromatic organic matter for containing two carboxyls, including terephthalic acid (TPA), One or more mixture in phthalic acid, adipic acid, azelaic acid；
The carbon number that two hydroxyls are connected in the aliphatic diol molecule is no less than 4, may be selected from BDO, 1, One or more mixtures in 6- hexylene glycols, diglycol, neopentyl glycol, 2- propyl group -1,6-HD；
The above-mentioned flexible package adhesive for solvent-free use of resistance to boiling, polyacrylate polyol passes through (methyl) in the B component Acrylate monomer obtains with hydroxy acryl acid ester monomer through radical polymerization.
The above-mentioned flexible package adhesive for solvent-free use of resistance to boiling, in the B component vitrifying of polyacrylate polyol turn Temperature is -25 DEG C -0 DEG C.
The above-mentioned flexible package adhesive for solvent-free use of resistance to boiling, polyether Glycols and/or polyether-tribasic alcohol in the B component Weight average molecular weight is 400-3000.
The above-mentioned flexible package adhesive for solvent-free use of resistance to boiling, the isocyanate terminated urethane prepolymer of the component A Isocyanate groups weight content is 13%-18%；
The polyol blends hydroxyl value of the B component is 50-180mgKOH/g.
A kind of preparation method of flexible package adhesive for solvent-free use of resistance to boiling provided by the invention, preparation process are as follows：
(1) by least two polyol blends in polyester diol, polyether Glycols and vegetable oil polyol in- 1-2 hours are removed water under the conditions of 0.09--0.1MPa, 110-120 DEG C, are cooled to 40-50 DEG C, under nitrogen protective condition, it is different to add two Cyanate esters, under the conditions of 70-75 DEG C reaction 3-4 hours obtain component A；
(2) polyether Glycols and/or polyether-tribasic alcohol are removed water into 1-2 under the conditions of -0.09--0.1MPa, 110-120 DEG C Hour, 75-80 DEG C is cooled to, nitrogen protection is lower by (methyl) acrylate monomer, hydroxy acryl acid ester monomer and initiator Instilled after well mixed in 3-4 hours in reaction system, being cooled to 25-30 DEG C after reaction 6-7 hours obtains B component；
(3) above-mentioned component A and B component are sufficiently mixed in room temperature to obtain the flexible package adhesive for solvent-free use of resistance to boiling.
Above-mentioned preparation method, component A is with B component according to mol ratio NCO：OH=1.1-1.8：1 ratio is mixed, institute It is 500-800mPa.s to obtain viscosity of the adhesive for solvent-free use under the conditions of 35-45 DEG C.
The flexible package adhesive for solvent-free use of resistance to boiling of the present invention, can be applied to include PET, PE, CPP, PA, BOPP, VMPET and any two kinds of materials of aluminium foil bonding.
Beneficial effect of the present invention is：
It is by ending isocyanate prepolymer component A and more by polyether Glycols and/or polyether-tribasic alcohol and polyacrylate Adhesive for solvent-free use is prepared in the B component of first alcohol composition, and viscosity of the adhesive under the conditions of 35-45 DEG C is 500- 800mPa.s, low coating weight (0.5-1.8g/m can be achieved2), high speed (300-500m/min) coating, nothing of the present invention Solvent cement curing peel strength is high, and through 135 DEG C, peel strength fall is less than 10% after boiling in 30 minutes, should Adhesive for solvent-free use suitable for the fields such as medicine, food the material such as various plastic sheetings, aluminizer it is compound.
Embodiment
The component A of the present invention is included by the polyester diol of 60-100 parts by weight, polyether Glycols and vegetable oil polyol In at least two glycol compositions and 100 parts by weight diisocyanate cpd react to obtain it is isocyanate-terminated poly- Urethane prepolymer；Component A viscosity at 25 DEG C is 1000-4000mPa.s, preferably 2000-3000mPa.s.
In the polyol blends that the B component is included, polyol blends gross weight ratio is shared by each polyalcohol Polyether Glycols and/or polyether-tribasic alcohol 50%-70%, polyacrylate polyol 30%-50%；The B component is at 25 DEG C When viscosity be 500-2000mPa.s, preferably 800-1800mPa.s.
PEPA containing two and above hydroxyl in the component A can be by dicarboxylic acids, aliphatic diol through polycondensation Reaction is made；
Aliphatic can be used or aromatic contain two carboxyls by wherein forming the dicarboxylic acids of PEPA in the component A Organic matter, including mixture one or more in terephthalic acid (TPA), M-phthalic acid, adipic acid, azelaic acid；Aliphatic two Alcohol can use molecule in connect two hydroxyls carbon number be no less than 4 glycol, may be selected from BDO, 1,6- oneself two One or more mixtures in alcohol, diglycol, neopentyl glycol, 2- propyl group -1,6-HD.
Diisocyanate cpd may be selected from but be not limited only to isoflurane chalcone diisocyanate, diphenyl in the component A One or more mixing in methane -4,4 '-diisocyanate, Carbodiimide-Modified MDI, hexamethylene diisocyanate Thing.
In order to improve the boiling resistance of adhesive and reduce system viscosity, contain polypropylene in heretofore described B component Acid esters polyalcohol, can be obtained through radical polymerization by (methyl) acrylate monomer and hydroxy acryl acid ester monomer
The glass transition temperature of polyacrylate polyol is -25 DEG C -0 DEG C in the B component.
Influence of the molecular weight of polymer to initial bonding strength is it is well known that in order to ensure adhesive of the present invention With good initial peeling force, the weight average molecular weight range of heretofore described polyacrylate polyol is 30000- 80000, preferably 45000-65000.
Wherein, the polyacrylate polyol can pass through (methyl) acrylate monomer and (methyl) third containing hydroxyl Olefin(e) acid ester monomer obtains through radical polymerization.Wherein (methyl) acrylate monomer can be selected but be not limited only to, methyl acrylate, Ethyl acrylate, butyl acrylate, isobutyl acrylate, glycidyl acrylate, the just own ester of acrylic acid, acrylate Ester, n-octyl, Isooctyl acrylate monomer, acrylic acid-2-ethyl caproite, isobornyl acrylate, lauryl acrylate, first Base methyl acrylate, EMA, butyl methacrylate, Isobutyl methacrylate, Glycidyl methacrylate are sweet Grease, the just own ester of methacrylic acid, cyclohexyl methacrylate, n octyl methacrylate, EHMA, methyl The mixing of one or more monomers in acrylic acid-2-ethyl caproite, isobornyl methacrylate, lauryl methacrylate Thing.Preferred methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, glycidyl in the present invention Ester, the just own ester of acrylic acid, cyclohexyl acrylate, n-octyl, Isooctyl acrylate monomer, acrylic acid-2-ethyl caproite, methyl Methyl acrylate, EMA, butyl methacrylate, Isobutyl methacrylate, methyl propenoic acid glycidyl Ester, the just own ester of methacrylic acid, cyclohexyl methacrylate, n octyl methacrylate, EHMA, methyl-prop It is more preferably different including methyl acrylate, ethyl acrylate, butyl acrylate, acrylic acid at least two in olefin(e) acid -2- ethylhexyls Butyl ester, glycidyl acrylate, the just own ester of acrylic acid, cyclohexyl acrylate, methyl methacrylate, methacrylic acid second Ester, butyl methacrylate, Isobutyl methacrylate, GMA, the just own ester of methacrylic acid, methyl The mixture of at least two monomers in cyclohexyl acrylate.
The hydroxy acryl acid ester monomer can be selected but be not limited only to, 2-Hydroxy ethyl acrylate, acrylic acid -3- hydroxyls Base propyl ester, acrylic acid -4- hydroxybutyls, methacrylic acid -2- hydroxy methacrylates, methacrylic acid -3- hydroxy propyl esters, metering system The mixture of one or more monomers in acid -4- hydroxybutyls.
The weight average molecular weight of PTMEG or polyether triol is 400-3000 in the B component.
In order to improve the curing peel strength of adhesive, the isocyanate terminated urethane of heretofore described component A is pre- The isocyanate groups weight content of polymers is 13%-18%；The polyol blends hydroxyl value of the B component is 50- 180mgKOH/g。
The present invention provides a kind of preparation method of the flexible package adhesive for solvent-free use of resistance to boiling, it is characterised in that：
(1) by least two polyol blends in polyester diol, polyether Glycols and vegetable oil polyol in- 1-2 hours are removed water under the conditions of 0.09--0.1MPa, 110-120 DEG C, are cooled to 40-50 DEG C, under nitrogen protective condition, it is different to add two Cyanate esters, under the conditions of 70-75 DEG C reaction 3-4 hours obtain component A；
(2) polyether Glycols and/or polyether-tribasic alcohol are removed water into 1-2 under the conditions of -0.09--0.1MPa, 110-120 DEG C Hour, 75-80 DEG C is cooled to, nitrogen protection is lower by (methyl) acrylate monomer, hydroxy acryl acid ester monomer and initiator Instilled after well mixed in 3-4 hours in reaction system, being cooled to 25-30 DEG C after reaction 6-7 hours obtains B component；
(3) above-mentioned component A and B component are sufficiently mixed in room temperature to obtain the flexible package adhesive for solvent-free use of resistance to boiling.
The component A is with B component according to mol ratio NCO：OH=1.1-1.8：1 ratio is mixed, and gained is solvent-free Viscosity of the adhesive under the conditions of 35-45 DEG C is 500-800mPa.s.
The flexible package adhesive for solvent-free use of resistance to boiling of the present invention, can be applied to include PET, PE, CPP, PA, BOPP, VMPET and any two kinds of materials of aluminium foil bonding.
Illustrate technical scheme, further description will be deployed by embodiment below, but listed embodiment is only Illustration is played, and is not intended to limit the scope of the present invention.
Properties of sample evaluation method：
Peel strength test：With reference to standard GB/T/T 2790-1995《180 ° of peeling strength test methods of adhesive are scratched Property material is to rigid material》In method tested under conditions of peeling rate 300mm/min, batten width 15mm.
Embodiment 1
It is 2000 polyester by the 25Kg weight average molecular weight for polymerizeing to obtain by adipic acid/diglycol/1,6-HD Dihydric alcohol, the polyoxypropyleneglycol of 75Kg weight average molecular weight 1000 remove water 2 under the conditions of -0.09--0.1MPa, 110-120 DEG C Hour, it is cooled to 40 DEG C, under nitrogen protective condition, adds 50Kg methyl diphenylene diisocyanates and 50Kg isophorones two are different The mixture of cyanate, be gradually heating to 75 DEG C reaction 3-4 hours measure NCO weight/mass percentage compositions for 13% when stop reaction, Room temperature is down to, obtains component A, 25 DEG C of viscosity are 1800mPa.s.
The polyoxypropyleneglycol that 70Kg weight average molecular weight is 1000 is removed under the conditions of -0.09--0.1MPa, 110 DEG C Water 2 hours, is cooled to 75 DEG C, under nitrogen protection by 14.1Kg n-butyl acrylate, 12.9Kg Isobutyl methacrylate, 2.4Kg GMA and 0.6Kg 2-hydroxyethyl methacry-late and 0.3Kg azodiisobutyronitrile Instilled after well mixed in 4 hours in reaction system, reaction is cooled to room temperature and obtains the B groups that hydroxyl value is 80mgKOH/g after 7 hours Point, 25 DEG C of viscosity 800mPa.s.
10KgA components and 13.5KgB components are well mixed (- NCO：- OH=1.6:1), 40 DEG C of viscosity are 550mPa.s, Compound, the spread 1.5g/m using solvent-free composite machine progress PET/PE2, Coating Speed 350m/min, PET/PE composite membrane Initial bonding strength is 0.7N/15mm, peeling force 4.5N/15mm after composite membrane cures 24 hours at 40 DEG C；Print is through 135 DEG C of steamings Composite membrane is apparent normal after boiling 30 minutes, peeling force 3.3N/15mm.
Embodiment 2
It is 2000 polyester binaries by the 40Kg weight average molecular weight for polymerizeing to obtain by adipic acid/1,6-HD/neopentyl glycol Alcohol, that 2 are removed water under the conditions of -0.09--0.1MPa, 110-120 DEG C is small for the 45Kg polyoxypropyleneglycol of weight average molecular weight 1000 When, it is cooled to 40 DEG C, under nitrogen protective condition, adds 50Kg methyl diphenylene diisocyanates and the isocyanide of 50Kg isophorones two The mixture of acid esters, be gradually heating to 75 DEG C reaction 3-4 hours measure NCO weight/mass percentage compositions for 15% when stop reaction, drop To room temperature, component A is obtained, 25 DEG C of viscosity are 2300mPa.s.
The polyoxypropyleneglycol that 60Kg weight average molecular weight is 600 is removed under the conditions of -0.09--0.1MPa, 110 DEG C Water 2 hours, 75 DEG C are cooled to, by 14Kg acrylic acid-2-ethyl caproite, 13.2Kg isobutyl under nitrogen protection The 2-hydroxypropyl acrylate of ester, 12Kg hexyl methacrylate and 0.8Kg is well mixed with 0.4Kg azodiisobutyronitrile Afterwards in 4 hours instill reaction system in, reaction 7 hours after be cooled to room temperature obtain hydroxyl value be 117mgKOH/g B component, 25 DEG C Viscosity 1000mPa.s.
10KgA components and 11.5KgB components are well mixed (- NCO：- OH=1.5:1), 40 DEG C of viscosity are 620mPa.s, Compound, the spread 1.8g/m using solvent-free composite machine progress PET/PE2, Coating Speed 350m/min, PET/PE composite membrane Initial peeling force 0.5N/15mm, peeling force 5.2N/15mm after composite membrane cures 24 hours at 40 DEG C；After 135 DEG C of boilings 30 minutes Composite membrane is apparent normal, peeling force 4.8N/15mm.
Embodiment 3
The weight average molecular weight that 55Kg is polymerize to obtain by terephthalic acid (TPA)/diglycol/neopentyl glycol is gathered for 2000 Ester polyol, 10Kg weight average molecular weight 1000 polyoxypropyleneglycol under the conditions of -0.09--0.1MPa, 110-120 DEG C Water removal 2 hours, is cooled to 40 DEG C, under nitrogen protective condition, adds 50Kg methyl diphenylene diisocyanates and the different Fo Er of 50Kg The mixture of ketone diisocyanate, be gradually heating to 75 DEG C reaction 3-4 hours measure NCO weight/mass percentage compositions for 18% when stop Reaction, is down to room temperature, obtains component A, 25 DEG C of viscosity are 2900mPa.s.
The polyoxypropyleneglycol that 50Kg weight average molecular weight is 400 is removed under the conditions of -0.09--0.1MPa, 110 DEG C Water 2 hours, is cooled to 75 DEG C, under nitrogen protection by 25Kg n-butyl acrylate, 10Kg n-octyl, 14Kg first Base glycidyl acrylate and 1Kg 2-hydroxyethyl methacry-late are well mixed rear 4 with 0.5Kg azodiisobutyronitrile Instilled in hour in reaction system, reaction is cooled to room temperature and obtains the B component that hydroxyl value is 139mgKOH/g after 7 hours, 25 DEG C viscous Spend 1300mPa.s.
10KgA components and 12.3KgB components are well mixed (- NCO：- OH=1.4:1), 40 DEG C of viscosity are 670mPa.s, Compound, the spread 1.7g/m using solvent-free composite machine progress PET/PE2, Coating Speed 350m/min, PET/PE composite membrane Initial peeling force 0.9N/15mm, peeling force 5.4N/15mm after composite membrane cures 24 hours at 40 DEG C；After 135 DEG C of boilings 30 minutes Composite membrane is apparent normal, peeling force 4.7N/15mm.
Embodiment 4
It is 2000 by the 45Kg weight average molecular weight for polymerizeing to obtain by terephthalic acid (TPA)/diglycol/1,4- butanediols PEPA, 50Kg castor oil polyhydric alcohol remove water 2 hours under the conditions of -0.09--0.1MPa, 110-120 DEG C, are cooled to 40 DEG C, under nitrogen protective condition, 100Kg IPDIs are added, being gradually heating to 75 DEG C of reaction 3-4 hours measures Stop reaction when NCO weight/mass percentage compositions are 15%, be down to room temperature, obtain component A, 25 DEG C of viscosity are 2500mPa.s.
The polyoxypropyleneglycol that 70Kg weight average molecular weight is 1000 is removed under the conditions of -0.09--0.1MPa, 110 DEG C Water 2 hours, is cooled to 75 DEG C, under nitrogen protection by 10.5Kg n-butyl acrylate, 12Kg Isobutyl methacrylate, 6.9Kg GMA and 0.6Kg 2-hydroxyethyl methacry-late and 0.3Kg azodiisobutyronitrile Instilled after well mixed in 4 hours in reaction system, reaction is cooled to room temperature and obtains the B groups that hydroxyl value is 80mgKOH/g after 7 hours Point, 25 DEG C of viscosity 800mPa.s.
10KgA components and 14KgB components are well mixed (- NCO：- OH=1.8:1), 40 DEG C of viscosity are 590mPa.s, are made Compound, the spread 1.8g/m that carries out PET/PE with solvent-free composite machine2, at the beginning of Coating Speed 400m/min, PET/PE composite membrane Beginning peeling force 0.6N/15mm, peeling force 5.8N/15mm after composite membrane cures 24 hours at 40 DEG C；It is multiple after 135 DEG C of boilings 30 minutes It is apparent normal to close film, peeling force 5.4N/15mm.
Embodiment 5
It is 2000 by the 25Kg weight average molecular weight for polymerizeing to obtain by terephthalic acid (TPA)/diglycol/1,4- butanediols PEPA, 30Kg polyoxypropyleneglycol, 45Kg castor oil polyhydric alcohol are in -0.09--0.1MPa, 110-120 DEG C of bar Removed water 2 hours under part, be cooled to 40 DEG C, under nitrogen protective condition, add 100Kg IPDIs, gradually heating To 75 DEG C of reaction 3-4 hours measure NCO weight/mass percentage compositions for 14% when stop reaction, be down to room temperature, obtain component A, 25 DEG C Viscosity is 1900mPa.s.
B component in 10kgA components and 13kg embodiments 4 is well mixed (- NCO：- OH=1.8:1), 40 DEG C of viscosity are 510mPa.s, spread 1.7g/m compound using solvent-free composite machine progress PET/PE2, Coating Speed 450m/min.PET/ The initial peeling force 0.5N/15mm of PE composite membranes, peeling force 5.5N/15mm after composite membrane cures 24 hours at 40 DEG C；135 DEG C of boilings Composite membrane is apparent normal after 30 minutes, peeling force 5.2N/15mm.
Embodiment 6
The weight average molecular weight that 55Kg is polymerize to obtain by terephthalic acid (TPA)/diglycol/neopentyl glycol is gathered for 2000 Ester polyol, 40Kg castor oil remove water 2 hours under the conditions of -0.09--0.1MPa, 110-120 DEG C, are cooled to 40 DEG C, nitrogen Under protective condition, add 100Kg IPDIs, be gradually heating to 75 DEG C reaction 3-4 hours measure NCO mass hundred Stop reaction when dividing content to be 15%, be down to room temperature, obtain component A, 25 DEG C of viscosity are 3100mPa.s.
B component in 10KgA components and 8Kg embodiments 3 is well mixed (- NCO：- OH=1.8:1), 40 DEG C of viscosity are 730mPa.s, spread 1.7g/m compound using solvent-free composite machine progress PET/PE2, Coating Speed 300m/min, PET/ The initial peeling force 0.9N/15mm of PE composite membranes, peeling force 5.9N/15mm after composite membrane cures 24 hours at 40 DEG C；135 DEG C of boilings Composite membrane is apparent normal after 30 minutes, peeling force 5.6N/15mm.
Comparative example 1
The polyoxypropyleneglycol that 100Kg molecular weight is 1000 is removed under the conditions of -0.09--0.1MPa, 110-120 DEG C Water 2 hours, is cooled to 40 DEG C, under nitrogen protective condition, adds 100Kg IPDIs, is gradually heating to 75 DEG C Reaction 3-4 hours, which are measured when NCO weight/mass percentage compositions are 15%, stops reaction, is down to room temperature, obtains polymer C, 25 DEG C of viscosity For 1100mPa.s.
B component in 10Kg polymer C and 14Kg embodiment 4 is well mixed (- NCO：- OH=1.8:1), 40 DEG C of viscosity It is compound using solvent-free composite machine progress PET/PE for 427mPa.s, spread 1.7g/m2, Coating Speed 350m/min, The initial peeling force 0.1N/15mm of PET/PE composite membranes, composite membrane cure 24 hours peeling force 2.7N/15mm at 40 DEG C；135 DEG C of steamings Composite membrane is apparent normal after boiling 30 minutes, peeling force 1.8N/15mm.
Comparative example 2
The weight average molecular weight that 100Kg is polymerize to obtain by terephthalic acid (TPA)/diglycol/neopentyl glycol is gathered for 2000 Ester polyol removes water 2 hours under the conditions of -0.09--0.1MPa, 110-120 DEG C, is cooled to 40 DEG C, under nitrogen protective condition, adds Enter 100Kg IPDIs, being gradually heating to 75 DEG C of reaction 3-4 hours measures NCO weight/mass percentage compositions as 15% When stop reaction, be down to room temperature, obtain polymer D, 25 DEG C of viscosity are 4500mPa.s.
B component in 10Kg polymer D and 8Kg embodiment 3 is well mixed (- NCO：- OH=1.8:1), 70 DEG C of viscosity It is compound using solvent-free composite machine progress PET/PE for 630mPa.s, spread 1.7g/m2, Coating Speed 300m/min, The initial peeling force 0.5N/15mm of PET/PE composite membranes, composite membrane cure 24 hours peeling force 5.0N/15mm at 40 DEG C；135 DEG C of steamings Composite membrane is apparent normal after boiling 30 minutes, peeling force 4.3N/15mm.
Comparative example 3
Component A in 10Kg embodiments 1 is well mixed with the polyoxypropyleneglycol of 8.8Kg molecular weight 1000 (- NCO：- OH=1.8:1), 40 DEG C of viscosity are 310mPa.s, and compound using solvent-free composite machine progress PET/PE, spread is 1.7g/m2, the initial peeling force 0.1N/15mm of Coating Speed 350m/min, PET/PE composite membrane, composite membrane is 24 small in 40 DEG C of curings When peeling force 2.1N/15mm；Composite membrane is apparent normal after 135 DEG C of boilings 30 minutes, peeling force 0.5N/15mm.
Because polymer C is different to be obtained by polyoxypropyleneglycol with isophorone isocyanate polymeric in comparative example 1 Cyanate blocked prepolymer, polyester-diol or vegetable oil polyol composition are not contained in composition, compared with embodiment 1-6, is compared The curing of example 1 peeling force is poor, and boiling peeling force declines substantially.
In comparative example 2 polymer D for the isocyanate-terminated prepolymer that is obtained using polyester diol, with containing polyethers The embodiment 1-6 of dihydric alcohol or vegetable oil polyol is compared, the adhesive viscosities prepared by the method in comparative example 2 it is high, it is necessary to It is heated to 70 DEG C to be just adapted to be coated with, process conditions require higher.
Polyacrylate polyol composition is not contained in the adhesive composition prepared by the methods described of comparative example 3, therefore, no Only cure peeling force it is poor, and after boiling between PET/PE adhesion strength decay most serious.
In summary, by isocyanate terminated urethane prepolymer A and by polyethers in embodiment provided by the present invention Adhesive for solvent-free use prepared by the polyol blends B of polyalcohol and polyacrylate polyol composition can ensure coating fluid tool While having compared with low viscosity, there is provided the excellent initial peeling force of composite membrane, curing peeling force, and composite membrane is through 135 DEG C of boilings 30 It can still keep that there is good peel strength after minute.

Claims (9)

  1. A kind of 1. flexible package adhesive for solvent-free use of resistance to boiling, it is characterised in that：Including component A and B component, wherein component A bag Include by least two polyol blends and diisocyanate in polyester diol, polyether Glycols and vegetable oil polyol Compound reacts obtained isocyanate terminated urethane prepolymer, B component include by polyether Glycols and/or polyether-tribasic alcohol with The polyol blends of polyacrylate polyol composition.
  2. 2. the flexible package adhesive for solvent-free use of resistance to boiling as claimed in claim 1, it is characterised in that：
    The component A include by the polyester diol of 60-100 parts by weight, polyether Glycols and vegetable oil polyol at least Two kinds of glycol compositions and the diisocyanate cpd of 100 parts by weight react obtained isocyanate terminated urethane pre-polymerization Thing, component A viscosity at 25 DEG C is 1000-4000mPa.s；
    In the polyol blends that the B component is included, polyol blends gross weight ratio shared by each polyalcohol is polyethers Dihydric alcohol and/or polyether-tribasic alcohol 50%-70%, polyacrylate polyol 30%-50%；The B component is glued at 25 DEG C Spend for 500-2000mPa.s.
  3. 3. the flexible package adhesive for solvent-free use of resistance to boiling as claimed in claim 2, it is characterised in that：
    The component A polyester diol can be made by dicarboxylic acids, aliphatic diol through polycondensation reaction,
    Wherein, the dicarboxylic acids is aliphatic or the aromatic organic matter for containing two carboxyls, including terephthalic acid (TPA), isophthalic two One or more mixture in formic acid, adipic acid or azelaic acid；
    In the aliphatic diol molecule connect two hydroxyls carbon number be no less than 4, selected from BDO, 1,6- oneself two One or more mixtures in alcohol, diglycol, neopentyl glycol or 2- propyl group -1,6-HD.
  4. 4. the flexible package adhesive for solvent-free use of resistance to boiling as claimed in claim 3, it is characterised in that：Polypropylene in the B component Acid esters polyalcohol is obtained by (methyl) acrylate monomer with hydroxy acryl acid ester monomer through radical polymerization.
  5. 5. the flexible package adhesive for solvent-free use of resistance to boiling as claimed in claim 4, it is characterised in that：Polypropylene in the B component The glass transition temperature of acid esters polyalcohol is -25 DEG C -0 DEG C.
  6. 6. the flexible package adhesive for solvent-free use of resistance to boiling as claimed in claim 5, it is characterised in that：Polyethers two in the B component The weight average molecular weight of first alcohol and/or polyether-tribasic alcohol is 400-3000.
  7. 7. the flexible package adhesive for solvent-free use of resistance to boiling as claimed in claim 6, it is characterised in that：
    The isocyanate groups weight content of the isocyanate terminated urethane prepolymer of the component A is 13%-18%；
    The polyol blends hydroxyl value of the B component is 50-180mgKOH/g.
  8. 8. a kind of method for preparing the flexible package adhesive for solvent-free use of resistance to boiling as described in claim any one of 1-7, its feature It is：
    (1) by least two polyol blends in polyester diol, polyether Glycols and vegetable oil polyol in -0.09-- 1-2 hours are removed water under the conditions of 0.1MPa, 110-120 DEG C, are cooled to 40-50 DEG C, under nitrogen protective condition, add diisocyanate Compound, under the conditions of 70-75 DEG C reaction 3-4 hours obtain component A；
    (2) polyether Glycols and/or polyether-tribasic alcohol are removed water into 1-2 hours under the conditions of -0.09--0.1MPa, 110-120 DEG C, 75-80 DEG C is cooled to, nitrogen protection is lower to mix (methyl) acrylate monomer, hydroxy acryl acid ester monomer with initiator Instilled after even in 3-4 hours in reaction system, being cooled to 25-30 DEG C after reaction 6-7 hours obtains B component；
    (3) above-mentioned component A and B component are sufficiently mixed in room temperature to obtain the flexible package adhesive for solvent-free use of resistance to boiling.
  9. 9. the preparation method of the flexible package adhesive for solvent-free use of resistance to boiling as claimed in claim 8, it is characterised in that：Component A and B Component is according to mol ratio NCO：OH=1.1-1.8：1 ratio is mixed, and gained adhesive for solvent-free use is under the conditions of 35-45 DEG C Viscosity be 500-800mPa.s.
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CN108624216B (en) * 2018-06-05 2021-05-04 广州慧谷化学有限公司 Water-based laser aluminizing transfer coating and preparation method thereof
CN108624216A (en) * 2018-06-05 2018-10-09 广州慧谷化学有限公司 A kind of aqueous laser aluminizing transfer paint and preparation method thereof
CN108977159A (en) * 2018-06-29 2018-12-11 汪辉 A kind of adhesive of resistance to boiling and preparation method thereof with good gas barrier property
CN109321193A (en) * 2018-08-07 2019-02-12 中国乐凯集团有限公司 Adhesive and its preparation method and application
CN113710764A (en) * 2019-04-24 2021-11-26 汉高股份有限及两合公司 Two-component solvent-free polyurethane laminating adhesive composition
WO2020215235A1 (en) * 2019-04-24 2020-10-29 Henkel Ag & Co. Kgaa Two-component solvent free polyurethane laminating adhesive composition
US20220162485A1 (en) * 2019-04-24 2022-05-26 Henkel Ag & Co. Kgaa Two-Component Solvent Free Polyurethane Laminating Adhesive Composition
EP3959282A4 (en) * 2019-04-24 2022-11-23 Henkel AG & Co. KGaA Two-component solvent free polyurethane laminating adhesive composition
CN113710764B (en) * 2019-04-24 2023-11-28 汉高股份有限及两合公司 Two-component solvent-free polyurethane laminating adhesive composition
CN112226193A (en) * 2020-10-19 2021-01-15 惠州市道科包装材料有限公司 Preparation method and application of water-based high-strength bi-component adhesive
CN114921212A (en) * 2022-06-01 2022-08-19 中国乐凯集团有限公司 Aluminum-plastic film adhesive, preparation method thereof and soft package battery
CN114921212B (en) * 2022-06-01 2023-10-27 中国乐凯集团有限公司 Plastic-aluminum film adhesive, preparation method thereof and soft package battery
CN115109556A (en) * 2022-06-29 2022-09-27 上海回天新材料有限公司 High-temperature-cooking-resistant solvent-free two-component polyurethane adhesive and preparation method thereof

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